Method and arrangement for separation of CO2 from combustion flue gas

ABSTRACT

A method for separating CO 2  from combustion exhaust gas includes discharging the CO 2 -containing combustion exhaust gas mass flow into the carbonator of a carbonate looping system having at least one carbonator and one calciner. Combining the CO 2  of the combustion exhaust gas mass flow with a carbonate-forming sorbent inside the carbonator to form a carbonate. Sending the carbonate as a carbonate-solids mass flow is sent to the calciner. Burning the carbonate at the carbonate-specific calcination temperature by the addition of heat provided by an additional firing that uses oxygen as the oxidant, whereby regenerated sorbent and a gas essentially containing CO 2  is formed. Sending the hot regenerated sorbent to the carbonator as a sorbent-solids mass flow for carbonization of CO 2 , and discharging the hot gas as gas mass flow. Replacing at least a portion of the heat of the additional firing with heat removed from the carbonate-solids mass flow or the gas mass flow in one or more heat exchangers prior to its entry into the calciner or inside the calciner.

BACKGROUND

This disclosure relates generally to a method and an arrangement for separating CO₂ from combustion exhaust gas. More particularly, this disclosure relates to a method and an arrangement for separating CO₂ from combustion exhaust gas that originates in a furnace through the combustion of carbon based fuels or wastes with the aid of air as an oxidizing agent.

Such a method has become known from the publication “Process Optimization in Postcombustion CO₂ Capture by means of Repowering and Reversible Carbonation/Calcination Cycle” by Luis M. Romeo et al., ENDESA, Spain, 8th Int. Conf. on Greenhouse Gas Control Technologies, June 2006, Trondheim, Norway.

In this known method, a large part of the CO₂ contained in the combustion exhaust gas is separated by means of a carbonate looping system or reversible carbonation/calcination cycle that is arranged downstream of the furnace (postcombustion) as seen in the direction of flow of the combustion exhaust gas, and is sent for further treatment. To separate the CO₂, the sorbent CaO, i.e., calcium oxide or unhydrated lime, is used and is carried in the loop inside the carbonate looping system. The CaO, which is produced or regenerated in the calciner at a temperature of 900-950° C., is sent at this temperature to the carbonator through a duct that connects the calciner with the carbonator. In the carbonator, into which the combustion exhaust gas containing the CO₂ is directed from the furnace and which has a circulating fluidized bed, at a temperature of approximately 650° C. the CaO absorbs a large part of the CO₂ contained in the combustion exhaust gas to the calcium carbonate CaCO3. The solids/gas mixture leaving the carbonator is sent to a separator in which the solids are separated from the combustion exhaust gas. The reduced-CO₂ combustion exhaust gas is sent into the atmosphere by means of a treatment facility that may be present, and the solids, essentially CaCO3 but also including ash, CaSO4 and CaO, are sent through ducts to the calciner. In the calciner, CaCO3 is heated or calcinated at a calcination temperature of 900-950° C., thereby creating one solid and one gaseous product. The solid product essentially exhibits CaO regenerated from the CaCO3 and the gaseous product essentially exhibits CO₂ and water. Since calcination takes place as an endothermic reaction, heat must be brought into the calciner in order to furnish the required calcination or reaction temperature. This takes place by means of an additional firing in the calciner, whereby coal is burned by means of the oxidizing agent or oxidant O2 and heat is thus brought into the calciner, which is equipped with a circulating fluidized bed. In order to avoid diluting the gaseous product that originates in the calciner, e.g., with nitrogen, thus making the separation of CO₂ more difficult, O2 is mandatorily used in place of air as the oxidant for the additional firing. The regenerated CaO is sent from the calciner to the carbonator as the sorbent with a product heat of approximately 900° C. With the same product heat, the gas product, which essentially contains CO₂, is diverted from the calciner and the CO₂ is sent for further treatment, and in this case cooled, compressed and transported for storage. The method described above runs continuously.

What has proven to be disadvantageous about the known method or arrangement is the fact that this method or arrangement is afflicted with a loss of efficiency of approximately 3 percentage points. This loss of efficiency can be essentially attributed to the calciner, which is equipped with additional firing and is thus fired, during which technically pure oxygen is used as the oxidant or oxidizing agent for burning the fuel, i.e., coal. In that regard, the production of oxygen for use as the oxidant in the calciner is associated with a high expenditure of energy that leads to the loss of approximately 3 efficiency percentage points.

The task of the invention is now to create a method for separating CO₂ from combustion exhaust gas that originates in a furnace through the combustion of carbon based fuels or wastes with the aid of air as an oxidizing agent that avoids the previously mentioned disadvantages. In particular, it is the task of the invention create a method for separating CO₂ from combustion exhaust gas that originates in a furnace through the combustion of carbon based fuels or wastes with the aid of air as an oxidizing agent, in which the need for additional firing, and thus the need for oxygen for the calciner, is reduced or can be eliminated entirely. It is also a task of the invention to suggest an arrangement for separating CO₂ from combustion exhaust gas that originates in a furnace through the combustion of carbon based fuels or wastes with the aid of air as an oxidizing agent.

SUMMARY

Through the inventive solution, a method and an arrangement for separating CO₂ from combustion exhaust gas that originates in a furnace through the combustion of carbon based fuels or wastes with the aid of air as an oxidizing agent is created which exhibit the following advantages:

-   -   Substantial reduction to complete elimination of the need for         additional firing and thus the need for oxygen for operating the         calciner,     -   Through the reduction or elimination of the need for oxygen, the         high expenditure of energy for the production of oxygen is         reduced or eliminated and the loss of efficiency of the facility         as a whole that occurs as the result of the production of oxygen         is substantially reduced.

An advantageous further development of the invention provides that the heated and sorbent-containing solids mass flow (F2) is utilized as the external heat source, and that the removal of a part of its contained heat takes place prior to the entry of the solids mass flow (F2) into the carbonator. As a result, the additional firing rate in the calciner, and thus the need for technical oxygen, declines. The expenditure of energy for the production of oxygen and thus the loss of efficiency is reduced in this way.

In an advantageous development of the invention, the heated and CO₂-containing gas mass flow (G2) that is leaving the calciner is utilized as the external heat source, and the removal of a part of its contained heat takes place prior to further treatment on the heat side. Through this measure, the additional firing rate in the calciner, and thus the need for technical oxygen, declines. The expenditure of energy for the production of oxygen and thus the loss of efficiency is reduced in this way.

In an advantageous further development of the invention, an external heat source that has a higher temperature than the operating temperature that prevails inside the carbonator is utilized as the external heat source, and the removal of at least a part of the contained heat of this external heat source takes place. As was already described above, the additional firing rate in the calciner, and thus the need for technical oxygen, declines in the same way. The expenditure of energy for the production of oxygen and thus the loss of efficiency is reduced in this way.

An advantageous development of the invention provides that natural or synthetic materials are used as the sorbent. Natural sorbents are inexpensive to acquire and can be disposed of or reused without difficulty. Synthetic materials can exhibit higher mechanical and chemical stability. The required circulating amount and the amount of fresh sorbents declines in this way.

Another advantageous further development of the invention provides that CaO is used as the absorption agent. CaO in the form of limestone is inexpensive to acquire and can be disposed of or reused without difficulty.

An advantageous further development of the invention provides that the heat exchange takes place regeneratively or recuperatively. This measure allows conventional and well-proven heat exchangers to be used for the required heat exchange.

In an advantageous further development of the invention, the heat transfer takes place by means of a heat transfer medium that exhibits favorable thermodynamic properties. Through this measure, a smaller mass flow is needed for circulation, as a result of which the effort for cycling the solid material can be kept low. This results in smaller plant dimensions and lower energy consumption for the transport of solid materials. In the same way, the overall sizes for the heat exchangers, line cross sections, etc., are smaller.

An advantageous development of the invention provides that helium or sodium is used as the heat transfer medium. These heat transfer media exhibit favorable thermodynamic properties with the advantages listed above.

In a practical further development of the invention, fossil fuels or biomass or wastes or a mixture of the substances mentioned above are used for the additional firing in the calciner. The fuel costs and thus the operating costs can be kept low through this measure.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure may be better understood and its numerous objects and advantages will become apparent to those skilled in the art by reference to the accompanying drawings in which:

FIG. 1 is a schematic representation of an arrangement for separation of CO₂ from combustion exhaust gas, i.e., a carbonate looping system downstream of a furnace (postcombustion).

DETAILED DESCRIPTION

FIG. 1 shows in schematic form an arrangement for separation of CO₂ from combustion exhaust gas, i.e., a carbonate looping system 2.

The carbonate looping system 2, which is arranged downstream, in the direction of flow of the combustion exhaust gas, of a furnace 1 (postcombustion), comprises a carbonator 3 with separator 6, as well as a heat exchanger 16, a calciner 4 with additional firing 5 and separator 7, a heat transfer system 8 or a heat exchanger 11, a heat transfer system 9 or a heat exchanger 12, as well as a heat transfer system 10 or a heat exchanger 13, which communicates with an external heat source, not shown. Provided additionally are heat exchanger devices 17, 18 downstream of the separators 6, 7 for cooling the gases.

The combustion exhaust gas G1 leaving the furnace 1 and containing CO₂, which originates in the furnace 1 through the combustion of carbon based fuels or wastes with the aid of air as an oxidizing agent, is sent to the carbonator 3 of the carbonate looping system 2 through a duct 14 and a fan 15. To separate a large part of the CO₂ contained in the combustion exhaust gas G1, the sorbent CaO, i.e., calcium oxide or quicklime, is used and is carried in the loop inside the carbonate looping system 2. The CaO, which is produced or regenerated in the calciner 4 at a temperature T_(calc) of 900-950° C., is sent at this temperature to the carbonator 3 by means of ducts 23, 24.

In the carbonator 3, which has a circulating fluidized bed, at a temperature T_(carbonator) of approximately 650° C. the CaO sorbent binds a large part of the CO₂ contained in the combustion exhaust gas G1 to the calcium carbonate CaCO₃. The solids/gas mixture leaving the carbonator 3 is sent via a duct 20 to a separator 6 in which the solids are separated from the combustion exhaust gas. The reduced-CO₂ combustion exhaust gas is sent via a duct 21 and a stack 19 or something similar into the atmosphere, whereby heat can still be removed from the reduced-CO₂ combustion exhaust gas by means of a heat exchanger 17 prior to discharge into the atmosphere. The solids, essentially containing CaCO₃ but also including ash, CaSO4 and CaO, are sent as carbonate-solids mass flow F1 through a duct 22 to the calciner 4.

In the calciner 4, CaCO₃ is burned or calcined at a temperature T_(calc) of 900-950° C., thereby creating one solid and one gaseous product. The solid product essentially exhibits CaO or sorbent regenerated from the CaCO₃ and the gaseous product essentially exhibits CO₂ and water. Since calcination takes place as an endothermic reaction, heat must be brought into the calciner 4 in order to furnish the required calcination or reaction temperature T_(calc). This takes place by means of an additional firing 5 in the calciner 4, whereby coal is burned by means of the oxidizing agent or oxidant O2 and heat QZ is thus brought into the calciner 4, which is equipped with a circulating fluidized bed. In order to avoid diluting the gaseous product that originates in the calciner 4, e.g., with nitrogen, thus making the separation of CO₂ more difficult, O₂ is mandatorily used in place of air as the oxidant for the additional firing. The regenerated CaO sorbent is diverted from the calciner 4 in the form of a solid product as well as gas product essentially containing CO₂ with a product heat of approximately 900° C., and is sent via a duct 23 to a separator 7 in which the sorbent or the solid product is separated from the gas. Starting from the separator 7, the hot sorbent at approximately 900° C. is sent in the form of the solids mass flow F2 via a duct 24 to the carbonator 3. The hot gas product, which is at approximately 900° C. and which essentially contains CO₂, is diverted in the form of gas mass flow G2 from the separator 7 and is sent via a duct 25 for further treatment, whereby the CO₂ can be cooled, compressed and transported for storage, for example. A heat exchanger 18, for example, can be used for the cooling. The method described above runs continuously.

According to the invention, the addition of heat QZ that took place by means of the additional firing 5 for maintaining the calcination temperature T_(calc) inside the calciner 4 is replaced in part or entirely, in that heat is removed from one or more heat source(s) and is sent through indirect heat exchange by means of heat exchangers 11, 12, 13 or through heat transfer by means of heat transfer systems 8, 9, 10 to the carbonate-containing carbonate-solids mass flow F1 prior to its entry into the calciner 4 or inside the calciner 4. FIG. 1 shows by way of example the removal of heat from three heat sources and by means of heat transfer systems 8, 9, 10, whereby part of the heat is removed from the sorbent-solids mass flow F2, which contains sorbent and is directed through duct 24, another part of the heat is removed from gas mass flow G2, which contains CO₂ and is directed through duct 25, and a further part of the heat is removed from an external heat source, not shown. In that regard, the external heat source has a higher temperature than the operating temperature T_(carbonator) that prevails in the carbonator 3. In place of the three heat sources listed by way of example, only two or one of the shown heat sources can also be used in order to partly or entirely replace the addition of heat QZ that took place by means of the additional firing 5 to maintain the calcination temperature T_(calc) inside the calciner 4. Moreover, heat exchangers 11, 12, 13 or a heat transfer system at a heat source and a heat exchanger at another heat source can be used in place of the heat transfer systems 8, 9, 10. For example, hot combustion exhaust gas from the furnace 1 or a hot medium from an external facility, not shown, can be utilized as an external heat source.

Through the inventive addition of heat from one or more heat source(s) to maintain the calcination temperature T_(calc) inside the calciner 4 and thus the partly or entirely replaced addition of heat QZ by means of the additional firing 5, a large part or all of the need for oxygen or O₂ (in the form of a technical gas) for the burning of the coal in the additional firing 5 can be saved. As a result, the expenditure of energy for the production of oxygen and the loss of efficiency of the facility that occurs with it can be substantially reduced.

Along with the CaO mentioned as the sorbent by way of example, natural or synthetic materials that form a carbonate during carbonizing in the carbonator 3 can also be used. These can be dolomites, limestones or pretreated natural sorbents, for example.

The heat exchangers 11, 12, 13 provided for the heat exchange can be regenerative or recuperative in design. In addition, the heat transfer systems 8, 9, 10 provided for the heat exchange possess a heat exchange medium that exhibits favorable thermodynamic properties, e.g., high thermal capacity cp. Helium or sodium is preferably used as the heat transfer medium.

It will be appreciated that various of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also that various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims. 

1. An improved method for separating CO₂ from combustion exhaust gas produced in a furnace through the combustion of carbon based fuels or wastes with air as an oxidizing agent, the method comprising the following steps: discharging the CO₂-containing combustion exhaust gas mass flow from the furnace into a carbonator of a carbonate looping system, the carbonate looping system including at least one carbonator and at least one calciner and having a carbonate-forming sorbent flowing within the loop; combining the sorbent with the CO₂ of the combustion exhaust gas mass flow within the carbonator to form a carbonate; sending the carbonate as a carbonate-solids mass flow to the calciner; burning the carbonate in the calciner at a carbonate-specific calcination temperature by adding heat produced by an additional firing that uses oxygen as the oxidant, whereby a regenerated sorbent and a gas substantially containing CO₂ are formed; sending the hot regenerated sorbent to the carbonator as a sorbent-solids mass flow for carbonization of CO₂; and sending the hot gas as gas mass flow for further treatment; wherein the improvement comprises replacing at least a portion of the additional firing with heat that is removed from one or more heat sources and is sent through indirect heat exchange to the carbonate-solids mass flow prior before the carbonate-solids mass flow enters the calciner or when the carbonate-solids mass flow is in the calciner.
 2. The method of claim 1, wherein the heated sorbent-solids mass flow is used as a heat source and the removal of a part of its contained heat takes place prior to the entry of the sorbent-solids mass flow into the carbonator.
 3. The method of claim 1, wherein the heated gas mass flow leaving at the separator downstream of the calciner is used as a heat source, and the removal of a part of its contained heat takes place prior to a further treatment on the heat side.
 4. The method of claim 1, wherein an external heat source that has a higher temperature than the operating temperature inside the carbonator is utilized as the heat source, and the removal of at least a part of the contained heat of this external heat source takes place.
 5. The method of claim 1, wherein natural or synthetic materials are used as the sorbent.
 6. The method of claim 1, wherein CaO is used as the absorption agent.
 7. The method of claim 1, wherein the heat exchange takes place regeneratively or recuperatively.
 8. The method of claim 1, wherein the heat transfer takes place by means of a heat transfer medium that exhibits favorable thermodynamic properties.
 9. The method of claim 8, wherein helium or sodium is used as the heat transfer medium.
 10. The method of claim 1, wherein fossil fuels or biomass or wastes or a mixture of the substances mentioned above are used for the additional firing in the calciner.
 11. An arrangement for separating CO₂ from combustion exhaust gas produced in a furnace through the combustion of carbon based fuels or wastes with air as an oxidizing agent, comprising: a carbonate looping system adapted to receive a flow of the combustion exhaust gas from the furnace, the carbonate looping system including at least one carbonator, at least one calciner, and a plurality of ducts adapted to carry a sorbent that forms carbonate between the carbonator and the calciner, whereby inside the carbonator the sorbent combines with the CO₂ of the combustion exhaust gas flow to form a carbonate, the carbonate as a carbonate-solids mass flow is sent to the calciner and is burned at a carbonate-specific calcination temperature by the addition of heat provided by an additional firing that uses oxygen as the oxidant, whereby regenerated sorbent and a gas essentially containing CO₂ is formed, the regenerated sorbent being sent to the carbonator as a sorbent-solids mass flow for carbonization of CO₂, and the hot gas being discharged as gas mass flow for further treatment; and at least one heat transfer system adapted to exchange heat from one or more heat sources to the carbonate-solids mass flow prior to its entry into the calciner or inside the calciner, whereby this heat replaces at least a portion of the heat from the additional firing to maintain the calcination temperature.
 12. The arrangement of claim 11, wherein the sorbent-solids mass flow conducted inside the duct is the heat source.
 13. The arrangement of claim 11, wherein the gas mass flow conducted inside the duct is the heat source.
 14. The arrangement of claim 11, wherein the heat source is an external heat source.
 15. The arrangement of claim 11, wherein the heat exchanger is a regenerative or recuperative heat exchanger. 